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X‐ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF4)

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Abstract

A 30 year-old PuF4 sample consisting of brown powder (PuF4-b) and pink granules (PuF4-p) was analyzed. X-ray diffraction shows the bulk is comprised of three compounds: PuF4, PuO2, and PuF4·1.6H2O. Broadening of PuF4 XRD peaks suggests possible \(\upalpha\)-damage. After annealing at 650 °C, crystalline PuF4 and PuO2 remain. Thermogravimetric analysis and differential scanning calorimetry—with simultaneous evolved gas analysis—of the separated PuF4-p and PuF4-b components reveal a distinct sequence of reactions. Dehydration occurs between ~ 90 and 300 °C. Exothermic annealing of the \(\upalpha\)-damage occurs in two stages: at 350–355 °C and at 555–558 °C. Hydrofluoric acid, fluorine and helium desorb during the first exotherm. Above 700 °C, PuF4 reacts with PuO2, resulting in oxygen release and mass loss.

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Acknowledgements

We thank 2 anonymous reviewers, and Mr. Gary Sevigny, and Drs. Sergey I. Sinkov, T. Gannon Parker and two anonymous Journal reviewers for reviewing this paper and suggesting useful to this manuscript. Dr. Steve Yarbro provided valuable input pertaining to the origin of the LANL PuF4.

Funding

This work was supported by the US Department of Energy through the Los Alamos National Laboratory. Los Alamos National Laboratory is operated by Triad National Security, LLC, for the National Nuclear Security Administration of U.S. Department of Energy (Contract No. 89233218CNA000001). This work was supported by the NA-22 Office of the US Department of Energy.

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Authors and Affiliations

  1. Materials Science and Technology, Nuclear Materials Science, MST-16, MS E574, Los Alamos National Laboratory, Los Alamos, NM, 87545, USA

    David M. Wayne

  2. Actinide Material Processing and Power, AMPP-3, MS E511, Los Alamos National Laboratory, Los Alamos, NM, 87545, USA

    Jared T. Stritzinger & Daniel J. Garcia

  3. Nuclear and Radiochemistry Team, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA, 99352, USA

    Amanda J. Casella, Lucas E. Sweet & Jordan F. Corbey

  4. Actinide Analytical Chemistry, C-AAC, MS E554, Los Alamos National Laboratory, Los Alamos, NM, 87545, USA

    E. Miller Wylie, Angela C. Olson & Jung Ho Rim

  5. Metal Production, PT-1, MS E551, Los Alamos National Laboratory, Los Alamos, NM, 87545, USA

    Lav Tandon

  6. Training and Mission Services, ORI-1, MS E523, Los Alamos National Laboratory, Los Alamos, NM, 87545, USA

    Daniel J. Garcia

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Contributions

Dr. David M. Wayne: conceptualization, methodology, investigation, formal analysis, resources, validation, data curation, writing (original draft), writing (review & editing), visualization. Dr. Jared Stritzinger: formal analysis, validation, data curation, resources, writing (review & editing), visualization. Dr. Amanda J. Casella: formal analysis, validation, data curation, resources, writing (review & editing). Dr. Lucas E. Sweet: investigation, data curation, writing. Dr. Jordan F. Corbey: investigation, data curation, writing. Mr. Daniel J. Garcia: investigation. Dr. E. Miller Wylie: investigation. Dr. Lav Tandon: funding acquisition, supervision, project administration, resources, writing (review & editing). Dr. Angela C. Olson: supervision, project administration, writing (review & editing), resources. Dr. Jung Ho Rim: investigation.

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Correspondence to David M. Wayne.

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Wayne, D.M., Stritzinger, J.T., Casella, A.J. et al. X‐ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF4). J Radioanal Nucl Chem 329, 741–756 (2021). https://doi.org/10.1007/s10967-021-07810-z

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